JP5158925B2 - Manufacturing method of printing substrate - Google Patents

Description

  The present invention relates to a method for producing a printing substrate used for producing an electronic member or an optical member. More specifically, a method for producing a printing substrate used for applying an electronic material for forming an electronic member or an optical material for forming an optical member on a substrate to be printed, a printing substrate obtained thereby, and the printing substrate The present invention relates to a method for producing an electronic member or an optical member using a material, and a method for regenerating the printing substrate.

  As a technique for forming a pattern with high accuracy in an insulating film of a semiconductor element, a liquid crystal display panel, etc., a method of combining material application by spin coating and photolithography is generally used, but pattern formation is to be performed in a large area. Then, there is a big problem that the manufacturing cost becomes high in photolithography. On the other hand, as a pattern forming technique, a method of forming a pattern in a large area with high accuracy by using printing techniques such as a screen printing method, an offset printing method, a flexographic printing method, and a gravure printing method is considered. These printing methods are suitable for forming a large number of patterns on a substrate, and are more advantageous than photolithography in terms of reduction in the amount of materials used and cost.

In recent years, the inkjet printing method has been applied to this field and has been developed. However, current problems include clogging of inkjet nozzles, fine patterning, printing speed, and the like.
From the viewpoint of printing speed, printing methods such as a flexographic printing method, an offset printing method, a gravure printing method, and a screen printing method have been applied and studied. Among them, flexographic printing is a method that uses a resin relief plate, and the ink is transferred to the surface of the convex part, and the convex part comes into contact with the surface of the printing material, so that the printing part is not stained. It is the method which has.

  The flexographic printing method is used for packaging materials such as cardboard, paper containers, paper bags, and flexible packaging films, wallpaper materials, building materials such as decorative boards, and label printing. Photosensitive resins are usually used for the production of printing plates used in flexographic printing, and a negative film is placed on the photosensitive resin using a liquid resin or a solid resin plate formed into a sheet. A method using photolithography in which light is irradiated through a negative film to cause a crosslinking reaction and then a non-crosslinked portion is washed away with a developer has been used. In the photosensitive resin plate that forms a pattern using photolithography, the thickness of the central portion of the photocured pattern is reduced due to curing shrinkage in the exposure process and extraction of uncured components into the developer in the development process. There are problems of unevenness in the thickness of the plate due to the cupping and warping of the plate where the outer periphery of the plate is warped. When a printing plate with low thickness accuracy is used, the film thickness of the pattern obtained by printing becomes non-uniform, and the performance of the obtained electronic component or optical member also becomes non-uniform. Therefore, in the system using the photosensitive resin plate, it has been a big problem to ensure the thickness accuracy of the obtained printing plate.

  As a specific example in which a printing method is applied in the production of an electronic member or an optical member, there is a method of printing an alignment film made of a polyimide resin on the surface of a glass substrate using a photosensitive resin relief plate. it can. The photosensitive resin relief plate has a negative film, a cover film, a liquid photosensitive resin, and a base film sandwiched between two glass plates. After irradiating light through the negative film to cause a crosslinking reaction, the uncrosslinked portion is developed. The method of washing off with liquid has been used. The photosensitive resin relief printing plate produced by such a method is not sufficiently uniform in the thickness of the convex portion, and the thickness of the peripheral portion of the convex portion is thicker than that of the central portion. Photocuring by photolithography (photoengraving technology) It has a cupping phenomenon due to shrinkage. Further, in the method of applying a liquid photosensitive resin on glass and photocuring it, it is difficult to form a photosensitive resin relief plate having a large size due to the deflection or thermal expansion of the glass.

  For example, in Patent Document 1, a pressure-sensitive adhesive layer having a substantially uniform thickness on the entire back surface (back surface of a base film layer) of a laminate composed of a photosensitive resin relief plate body and a base film layer, A method of reducing the cupping phenomenon of the photosensitive resin relief plate body by bonding and laminating and laminating a metal plate or synthetic resin plate with a flat surface is described, but the process is complicated and air bubbles are stuck at the time of bonding. There is a problem that the thickness accuracy of the printing plate is reduced. Moreover, in patent document 2 and patent document 3, a micro pattern is produced on the surface of the photosensitive resin relief plate formed using photolithography, and it is used for application | coating of a liquid crystal aligning film. In the manufacturing process of the minute pattern formed on the surface, even if extremely small dust or foreign matter exists on the exposure mask, it appears as a defect, so exposure in a very high clean environment is essential, The equipment required to maintain the environment is also large and extremely expensive. Defects formed by dust and foreign matter have been a major problem that is reproduced as defective printing in the subsequent printing process. Further, the production yield of the photosensitive resin relief printing plate produced was never high. Therefore, forming a photosensitive resin relief plate having such a fine pattern on the surface requires a large and expensive equipment investment for the apparatus, and the amount of photosensitive resin relief plate discarded as a defective product is also large. Met. In addition, it is impossible to reuse the photosensitive resin relief printing plate once used in printing and having the surface pattern worn down or missing, and it must be treated as waste.

  In addition, solvent components in electronic materials or optical materials used to form conductors, semiconductors, and insulators of electronic and optical members can swell the printing substrate or extract constituent components in the printing substrate. There have been problems such as significant changes in physical properties, and ensuring solvent resistance has been a major issue. In the photosensitive resin plate using photolithography, the function of forming a fine pattern is particularly important. Therefore, it is important to have good dissolution or dispersion characteristics of the uncured resin in the developer used in the development step, and there are limitations on materials that can be selected in the design of the photosensitive resin composition. Therefore, it cannot be said that the solvent resistance characteristics with respect to a wide variety of solvent components in electronic materials or optical materials are sufficient.

In recent years, a method of forming a concave pattern on a resin surface by a laser engraving method has progressed. However, the deeper the concave pattern is, the longer it takes to process. Also, when the resin is melted or removed with a laser beam to form a concave pattern, a large amount of highly sticky liquid residue is generated, and the surface of the printing substrate is contaminated or adhered due to the adhesion of the generated liquid residue. There was also a problem that the property of changed.
In any of the conventional techniques, a printing substrate having high solvent resistance and high plate thickness accuracy for applying an electronic material or an optical material to produce an electronic member or an optical member can be easily obtained in a short time. There was no known method that could be formed.
Japanese Patent No. 3496086 Japanese Patent No. 3315063 Japanese Patent No. 3376908

  An object of this invention is to provide the manufacturing method of the printing base material with high plate | board thickness precision used suitably for printing of an electronic material or an optical material. Furthermore, an object of the present invention is to provide a method for easily producing a printing substrate having high plate thickness accuracy and high solvent resistance, which is suitably used for printing electronic materials or optical materials. Moreover, this invention provides the manufacturing method of the electronic material member or optical material member in which the electronic material or the optical material layer was provided uniformly, and the method of reproducing | regenerating the used printing base material simply. Another purpose.

As a result of studying the inventors, paying attention to the fact that forming a concave pattern on a cured resin formed into a cylindrical shape is effective for obtaining a printing substrate with high plate thickness accuracy, the concave pattern Prior to formation, the thickness and roughness of the cured resin layer are adjusted on the surface of the cured resin layer using at least one method selected from cutting, grinding, and polishing , and the formed resin Cutting a groove-shaped concave pattern formed on the surface of the cured product layer, which exists between the convex patterns that are printed patterns arranged in the major axis direction and the circumferential direction of the cylindrical support. , be carried out by grinding like, further, by applying a photosensitive resin composition into a cylindrical shape, it found that high printing substrate of the plate thickness accuracy can be obtained.

That is, the present invention is as follows.
1. (A) a step of forming a cured resin layer on the surface of the cylindrical support, (b) at least one method selected from cutting, grinding, and polishing on the surface of the obtained cured resin layer. , the step of adjusting the thickness of the cured resin layer, the roughness, (c) a concave pattern formed on the formed cured resin layer table surface, the major axis direction and the circumferential direction of the cylindrical support present between the pattern of the convex portion is a print pattern sequence comprises a concave pattern forming step of forming a groove-like concave pattern, a method of forming a concave pattern of the step (c), cutting, Ken or cutting Ri least one method der are al selected, the cylindrical support body of the step and the cylindrical support to form a groove-shaped concave patterns while rotating in the circumferential direction to secure the cylindrical support Forming a groove-like concave pattern in the major axis direction of It said groove-like concave pattern, width 0.05mm or less than 50mm, a method of manufacturing a printed substrate, characterized in 20mm following linear pattern der Rukoto more depth 0.05mm to.
2. The more step (b), the thickness accuracy of the resin cured product layer and 30μm or less, the 1. Method of manufacturing a printed substrate according to.
3. The step (a) includes (d) a step of winding the sheet-like support around the surface of the cylindrical support, and (e) applying a resin composition onto the sheet-like support wound around the surface of the cylindrical support and applying a resin. forming a composition layer, after (f) curing the resin composition layer formed may include a step of forming a cured resin layer, and wherein step (c), (g) of the cured resin layer Including the step of processing into a sheet by cutting in the longitudinal direction of the cylindrical support. Or the manufacturing method of the printing base material of 2 .
4). 2. The resin composition in the step (e) is a photosensitive resin composition, and the curing in the step (f) is curing by irradiating the photosensitive resin composition with high energy rays . The manufacturing method of the printing base material as described in 2.
5. The photosensitive resin composition is liquid at 20 ° C., has at least one molecular skeleton selected from a polycarbonate skeleton, a polyester skeleton, and an aliphatic hydrocarbon skeleton, and includes a urethane bond, an amide bond, and an imide bond. 3. A compound having at least one type of bond selected . The manufacturing method of the printing base material as described in 2.
6). The method of coating the resin composition on the sheet-like support is at least one method selected from a doctor blade coating method, a die extrusion method, a spray coating method, a gravure coating method, and a roll coating method. The above 3. ~ 5. The manufacturing method of the printing base material in any one of.
7). In step (b), the surface of the cured resin layer, cutting, grinding, using at least one method selected from grinding, the thickness of the cured resin layer, the step of adjusting the roughness Is performed while rotating the cylindrical support in the circumferential direction. ~ 6. The manufacturing method of the printing base material in any one.
8). Above 1. ~ 7. The printing base material produced using the method in any one of.
9. 7. The above-mentioned 8, which is used for applying a liquid electronic material or optical material . The printing base material as described in.
10. Above 8. A step of attaching the printing base material described in the above to a cylindrical printing cylinder of a printing machine, a step of attaching a liquid electronic material or optical material to the surface of the printing base material, and transferring it onto the printing base material, the electronic material or A method for producing an electronic member or an optical member, comprising a step of immobilizing an optical material on the substrate to be printed.
11. The electronic material or the optical material contains at least one compound selected from an aromatic hydrocarbon compound, a nitrogen-containing hydrocarbon compound, an ester compound, an amide compound, a glycol monoether compound, and a halogen-containing hydrocarbon compound as a total solvent component The above-mentioned 10. characterized by containing 20 wt% or more . A method for producing the electronic member or the optical member according to the above.
12 10. The above-mentioned 10. The substrate to be printed is at least one kind of substrate selected from a glass plate, a ceramic plate, a film, a metal plate, and paper . Or 11. A method for producing the electronic member or the optical member according to the above.
13. The above-mentioned 8. used in the printing process . After the printing substrate according to the above is mounted on a cylindrical support, the surface of the printing substrate is adjusted again while rotating the cylindrical support in the circumferential direction. Playback method.

  According to the present invention, a printing substrate having high plate thickness accuracy and high solvent resistance can be produced in a short time. Furthermore, according to this invention, it is also possible to manufacture a printing base material, reproducing | regenerating a used printing base material.

Hereinafter, preferred embodiments of the present invention will be described in more detail.
[Manufacturing method of printing substrate]
The printing substrate of the present invention includes (a) a step of forming a cured resin layer on the surface of a cylindrical support, (b) a step of adjusting the surface of the obtained cured resin layer, and (c) an adjusted resin. It is manufactured through a step of forming a concave pattern on the surface of the cured product layer.
In the step (a) of forming the cured resin layer on the cylindrical support, a method of applying an uncured resin composition on the cylindrical support and then curing, or a separately formed sheet-shaped resin For example, a method of winding the cured product layer on a cylindrical support can be employed. Examples of the cylindrical support used include a metal cylinder, a rubber roll, and a fiber reinforced plastic sleeve.

  From the viewpoint of further improving the plate thickness accuracy, it is preferable to harden after applying the resin composition in a cylindrical shape in the step (a). For example, in the case of using a sheet-like support, the step (a) includes the step (d) the step of winding the sheet-like support around the surface of the cylindrical support, and the step (e) wound around the surface of the cylindrical support. It is preferable to include a step of applying a resin composition on a sheet-like support to form a resin composition layer, and (f) a step of curing the formed resin composition layer to form a cured resin layer. Through a process of forming a cylindrical resin cured product layer and then processing into a sheet-shaped resin cured product layer, it is possible to obtain a printing substrate having extremely high thickness accuracy and a uniform surface roughness. It becomes possible.

The method of applying the resin composition is preferably at least one method selected from a doctor blade coating method, a die extrusion method, a spray coating method, a gravure coating method, and a roll coating method.
When using a sheet-like support, the cylindrical support has a mechanism for holding at least one end of the sheet-like support, or for fixing the sheet-like support to at least a part of the surface of the cylindrical support. It is preferable that an adhesive layer is formed. As a mechanism for holding at least one end of the sheet-like support, a clamp mechanism for clamping the sheet-like blanket to the blanket cylinder in an offset printing machine, and a clamp mechanism for clamping the sheet-like printing plate to the plate cylinder are concrete. An example is given. Details of these clamping mechanisms are described in “Introduction to New Printing Machinery” (published October 31, 2001, pages 69 to 72) published by the Japan Printing Society Press. In addition, the adhesive layer for fixing the sheet-like support may be formed on the entire surface of the cylindrical support, but there is a possibility that air may be involved when the sheet-like support is attached. Therefore, it is more preferable that the adhesive layer is formed in a band shape in the major axis direction of the cylindrical support. The tackiness of the surface of the adhesive layer is not particularly limited, but it is necessary that the tackiness is such that the sheet-like support does not peel off at least when the cylindrical support is rotated in the circumferential direction.

In the case of using a sheet-like support, the production method of the present invention preferably includes a step of g) processing the cured resin layer into a sheet by cutting it in the long axis direction of the cylindrical support. As a method of cutting the resin cured product layer in the step (g), a method of cutting by moving the blade of the blade in the long axis direction of the cylindrical support, a long axis of the cylindrical support using laser light such as an infrared laser, etc. Examples of the method include cutting by moving in the direction.
Examples of the step (b) of adjusting the surface of the cured resin layer include a step of making the thickness of the cured resin layer uniform and a step of making the surface roughness of the cured resin layer uniform. Examples of methods for adjusting the surface of the cured resin layer include cutting, grinding, and polishing methods. These methods can be used in combination. In the step of adjusting the surface, it is preferable to perform cutting, grinding, and polishing while rotating the cylindrical support in the circumferential direction. In these methods, it is preferable to use an abrasive cloth or abrasive paper such as a commonly used tool, a milling blade, a ceramic grinding wheel, a grinding roll, or sandpaper as a jig.

  The material of the jig used for cutting, grinding, and polishing can be changed depending on the type of the cured resin to be processed and the finish roughness of the surface. Further, it is possible to perform processing such as cutting, grinding, and polishing by a dry method, but it is preferable to perform it by a wet method from the viewpoint of the finished state and the processing speed. In the case of wet processing, it is more preferable to use an aqueous processing solution in consideration of the handling property of the processing solution and the ease of post-processing. Various types of roughness can be obtained for grinding cloths and grinding papers such as grinding wheels, grinding rolls, and sand papers used in the grinding and polishing processes. When ceramics or diamond particles are attached to the surface, the finished roughness of the surface can be controlled by the particle diameter. In particular, in the polishing process, the cylindrical support is rotated by contacting the surface with the surface while rotating the cylindrical support in the circumferential direction and simultaneously polishing in the circumferential direction. An apparatus capable of performing polishing in the long axis direction can also be obtained. Further, the surface to be polished can be brought into contact with the new polishing paper while gradually feeding the polishing paper in a roll-to-roll manner. Blasting may be used as a polishing method. In the blast processing, a method of spraying fine particles such as ceramics and metal on the surface to be processed at high speed can be mentioned. Further, a wet brass method in which a liquid processing liquid containing fine particles is sprayed may be used. Moreover, in the cutting method, the method etc. which spray high pressure water on a to-be-processed surface in the shape of a beam can also be implemented.

In the cutting, grinding, and polishing steps, waste is generated and is preferably removed. When carried out by a wet method, the removal of waste is relatively easy. For the adhesive residue remaining on the surface, a cleaning solution that easily disperses or dissolves the resin composition to be used can be used. As the cleaning liquid, a treatment liquid containing an aqueous surfactant is preferable. Preferred surfactants include sodium dodecylbenzene sulfonate, polyoxyethylene nonyl octyl phenyl ether, sodium polyoxyethylene nonyl phenyl ether sulfonate, sodium lauryl ether sulfonate, and the like.
The thickness accuracy of the cured resin layer after the surface adjustment in the step (b) is preferably 30 μm or less. More preferably, it is 20 micrometers or less, More preferably, it is 10 micrometers or less. A thickness of 30 μm or less is preferable because printing with higher accuracy is possible and printing pressure at a lower printing pressure is also possible. In the thickness accuracy of the present invention, the thickness accuracy of 30 μm means ± 15 μm with respect to the average value of thickness measurement. When adjusting the surface of the cured resin layer having low hardness, it is preferable to cool the surface of the cured resin layer or cool the cylindrical support. As an indication of a cured resin having a low hardness, a range of 10 degrees to 50 degrees in Shore A hardness can be given.

  In the manufacturing method of this invention, the process (c) which forms a concave pattern in the at least 1 location of the formed resin cured material layer surface after the said process (b) is included. Here, the concave pattern formed on the surface is a groove-like pattern that exists between the arranged patterns, and does not include a thin portion that exists at the edge of the printing substrate as shown in FIG. And The width of the concave pattern is preferably 0.05 mm or more and 50 mm or less on the surface of the printing substrate from the point that the concave pattern can be formed in an extremely short time. A more preferable range is 0.1 mm or more and 20 mm or less, and further preferably 0.2 mm or more and 10 mm or less. The cross-sectional shape of the concave pattern may be any of an inverted triangle, an inverted trapezoid, a quadrangle, a polygon, a semicircular, and a semielliptical. Although there is no restriction | limiting in particular in the depth of a pattern, when applying an electronic material or an optical material, 0.05 mm or more and 20 mm from the point which only the pattern surface which is the convex of a printing base material contacts a to-be-printed base material. Or less, more preferably from 0.1 mm to 10 mm, and even more preferably from 0.2 mm to 5 mm. The depth of the concave pattern may vary depending on the location of the printing substrate. The pattern of convex portions on the surface of the printing substrate is preferably a regularly arranged pattern. The formed concave pattern is preferably a linear pattern. A plurality of the recessed patterns formed may intersect.

In the present invention, the formation of the concave pattern in the step (c) is performed by at least one method selected from cutting, grinding, and polishing. By using these methods, the processing speed is remarkably improved as compared with laser engraving or the like. Among the above methods, a cutting method using a cutting tool, a milling blade and the like, and a grinding method using a cylindrical grinding wheel are particularly preferable from the viewpoint of processing speed. Furthermore, it is preferable that these processes are performed with the position controlled by a computer. The concave pattern may be formed by a single cutting, grinding, and polishing operation, or may be formed by increasing the depth little by little in a plurality of times.
In the manufacturing method of the present invention, compared to the method of forming a concave pattern on a flat plate, from the viewpoint of ensuring the depth accuracy of the concave pattern to be formed, in step (c), the cylindrical support body is circumferentially arranged It is preferable to further include a step of forming a concave pattern while rotating and / or a step of fixing the cylindrical support and forming a concave pattern in the longitudinal direction of the cylindrical support.

Examples of the cured resin used in the present invention include a cured photosensitive resin obtained by irradiating and curing a photosensitive resin composition with high energy rays, a cured resin obtained by thermally curing a thermosetting resin, and rubber. Examples thereof include a cured rubber material obtained by vulcanizing a system material. From the viewpoint of curing speed, a photosensitive resin composition is particularly preferable. Examples of the high energy rays used for curing the photosensitive resin composition include light having an emission wavelength in the ultraviolet region and visible light region, an electron beam, X-rays, and a molecular beam.
The photosensitive resin composition particularly preferred as the resin composition used in the present invention is described below.
The photosensitive resin composition used in the present invention preferably contains a resin (α) having a number average molecular weight of 1,000 to 500,000 and an organic compound (β) having a polymerizable reactive group having a number average molecular weight of less than 1,000.
The photosensitive resin composition may be liquid or solid at 20 ° C., but is preferably liquid at 20 ° C. for ease of moldability.

  The resin (α) may be liquid or solid at 20 ° C., but is preferably a liquid resin at 20 ° C. from the viewpoint of moldability. The liquid resin here means a polymer that has the property of being easily deformed by flow and solidified into a deformed shape by cooling. When an external force is applied, the liquid resin is instantly deformed according to the external force. When the external force is removed, the term corresponds to an elastomer having a property of restoring the original shape in a short time. When the resin (α) is a liquid resin at 20 ° C., the photosensitive resin composition also becomes a liquid at 20 ° C., and obtains good thickness accuracy and dimensional accuracy when molded into a sheet or cylinder. Can do. When the liquid photosensitive resin is used, the viscosity of the photosensitive resin composition is preferably 10 Pa · s or more and 10 kPa · s or less at 20 ° C. More preferably, it is 50 Pa · s or more and 5 kPa · s or less. If the viscosity is 10 Pa · s or more, the mechanical strength of the produced printing substrate is sufficient, and the shape can be easily maintained and processed even when it is formed into a cylindrical shape. If the viscosity is 10 kPa · s or less, it is easy to be deformed and processed easily without increasing the temperature. It is easy to form into a sheet-like or cylindrical printing substrate, and the process is simple. In particular, in order to obtain a printing substrate with high thickness accuracy, the viscosity of the photosensitive resin composition is 100 Pa · s or more, more preferably 200 Pa · s or more, and even more preferably so that the phenomenon does not cause dripping due to gravity. Is desirably a photosensitive resin composition having a relatively high viscosity of 500 Pa · s or more.

  The number average molecular weight of the resin (α) is from 1,000 to 500,000, more preferably from 5,000 to 200,000, and even more preferably from 10,000 to 100,000. If the number average molecular weight of the resin (α) is 1000 or more, an original plate produced by crosslinking later maintains strength, and can be used repeatedly when used as a printing substrate. The upper limit of the number average molecular weight of the resin (α) is preferably 500,000 or less. If it is 500,000 or less, the viscosity of the photosensitive resin composition will not increase excessively, and a complicated processing method such as heat extrusion is not necessary when forming into a sheet or cylinder. The number average molecular weight referred to here is a value measured by gel permeation chromatography, calibrated with polystyrene having a known molecular weight, and converted.

  The resin (α) may have a polymerizable unsaturated group in the molecule. Particularly preferred are polymers having an average of 0.7 or more polymerizable unsaturated groups per molecule. When the average is 0.7 or more per molecule, the printing original plate obtained from the photosensitive resin composition is excellent in mechanical strength, and the relief shape is difficult to collapse during laser engraving. Furthermore, its durability is good, and it can withstand repeated use, which is preferable. Considering the mechanical strength of the printing original plate, the polymerizable unsaturated group of the resin (α) is preferably 0.7 or more per molecule, and more preferably more than 1. The abundance ratio of the polymerizable unsaturated group in the resin (A) can be quantified using a high resolution nuclear magnetic resonance spectrum method (NMR method). The term “intramolecular” as used herein includes the case where a polymerizable unsaturated group is directly attached to the terminal of the polymer main chain, the terminal of the polymer side chain, the polymer main chain, or the side chain. The polymerizable unsaturated group of the present invention is defined as a polymerizable unsaturated group involved in a radical or addition polymerization reaction. Preferable examples of the polymerizable unsaturated group involved in the radical polymerization reaction include a vinyl group, an acetylene group, an acrylic group, and a methacryl group. Preferred examples of the polymerizable unsaturated group involved in the addition polymerization reaction include cinnamoyl group, thiol group, azide group, epoxy group that undergoes ring-opening addition reaction, oxetane group, cyclic ester group, dioxirane group, spiroorthocarbonate group, spiro An ortho ester group, a bicyclo ortho ester group, a cyclic imino ether group and the like can be mentioned.

  As a method for introducing a polymerizable unsaturated group into the resin (α) molecule, for example, a method in which a polymerizable unsaturated group is directly introduced at the molecular end may be used. Of the above components having a molecular weight of about several thousand having a plurality of reactive groups such as groups, epoxy groups, carboxyl groups, acid anhydride groups, ketone groups, hydrazine residues, isocyanate groups, isothiocyanate groups, cyclic carbonate groups, and ester groups. After reacting with a binder having a plurality of groups capable of binding to the reactive group (for example, polyisocyanate in the case of a hydroxyl group or an amino group), the molecular weight is adjusted and converted to a terminal binding group. A method such as a method of introducing a polymerizable unsaturated group at a terminal by reacting with an organic compound having a polymerizable unsaturated group and a group that reacts with a bonding group is preferred.

  In particular, when a material is applied onto a hard substrate to be printed such as glass or ceramics, the resin (α) is partially a liquid resin having a glass transition temperature of 20 ° C. or lower, more preferably a glass transition temperature of 0 ° C. or lower. It is preferable to use a liquid resin. Examples of such liquid resins include hydrocarbons such as polyethylene, polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated poisoprene, polyesters such as adipate and polycaprolactone, and polymers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples include ethers, aliphatic polycarbonates, silicones such as polydimethylsiloxane, polymers of (meth) acrylic acid and / or derivatives thereof, and mixtures and copolymers thereof. The content is preferably 30 wt% or more based on the entire resin (α). In particular, from the viewpoint of resistance to a solvent contained in an electronic material or an optical material, it has at least one molecular skeleton selected from a polycarbonate skeleton, a polyester skeleton, and an aliphatic hydrocarbon skeleton, and has a urethane bond, an amide bond, and an imide. It is preferable to contain a compound having at least one type of bond selected from bonds.

  The organic compound (β) is preferably a compound having a number average molecular weight of less than 1000 and having a polymerizable reactive group in the molecule. The polymerizable reactive group is a functional group that contributes to radical polymerization reaction, addition polymerization reaction, and ring-opening addition polymerization reaction. Preferable examples of the polymerizable reactive group involved in the radical polymerization reaction include a vinyl group, an acetylene group, an acrylic group, and a methacryl group. Preferred examples of the polymerizable reactive group involved in the addition polymerization reaction include a cinnamoyl group, a thiol group, an azide group, an epoxy group that undergoes a ring-opening addition reaction, an oxetane group, a cyclic ester group, a dioxirane group, a spiro ortho carbonate group, and a spiro ortho group. Examples include an ester group, a bicycloorthoester group, and a cyclic imino ether group. Considering the ease of dilution with the resin (α), the number average molecular weight is preferably 1000 or less. Examples of the organic compound (β) include olefins such as ethylene, propylene, styrene and divinylbenzene, acetylenes, (meth) acrylic acid and derivatives thereof, haloolefins, unsaturated nitriles such as acrylonitrile, (meth) acrylamide and Derivatives thereof, allyl compounds such as allyl alcohol and allyl isocyanate, unsaturated dicarboxylic acids such as maleic anhydride, maleic acid and fumaric acid and derivatives thereof, vinyl acetates, N-vinylpyrrolidone, N-vinylcarbazole, cyanate esters, etc. However, (meth) acrylic acid and its derivatives are preferred examples from the viewpoints of the abundance of their types and price.

The molecular structure of the organic compound (β) includes an alicyclic hydrocarbon skeleton such as a cycloalkyl skeleton, a bicycloalkyl skeleton, a cycloalkene skeleton, and a bicycloalkene skeleton, a benzyl group, a phenyl group, a phenoxy group, a naphthyl group, and a pyrenyl group. Aromatic hydrocarbon skeleton, alkyl group, halogenated alkyl group, alkoxyalkyl group, hydroxyalkyl group, aminoalkyl group, tetrahydrofurfuryl group, molecular structure having glycidyl group, alkylene glycol, polyoxyalkylene glycol, polyalkylene Examples thereof include ester compounds of polyhydric alcohols such as glycol and trimethylolpropane.
In the present invention, the organic compound (β) having a polymerizable reactive group can be selected from one or more types according to the purpose. When an electronic material or an optical material is applied as a printing substrate, at least one long-chain aliphatic, alicyclic or aromatic derivative is used as an organic compound used to suppress swelling with respect to a solvent contained in the electronic material or optical material. It is preferable to have more than one type.

  A method for measuring the number average molecular weight (Mn) of the organic compound (β) of the present invention will be described. It is dissolved in a solvent in which the organic compound (β) is dissolved, analyzed by gel permeation chromatography (GPC method), and converted to standard polystyrene with a known molecular weight to calculate the number average molecular weight (Mn). This method is used for compounds having a wide molecular weight distribution. As a measure for the molecular weight distribution, the ratio of the number average molecular weight (Mn) and the weight average molecular weight (Mw) calculated simultaneously with Mn, that is, the polydispersity (Mw / Mn) is used. When the polydispersity is 1.1 or more, the number average molecular weight determined by the GPC method is adopted on the assumption that the molecular weight distribution is wide. In addition, those having a polydispersity of less than 1.1 have a very narrow molecular weight distribution, so that molecular structure analysis is possible, and the number average molecular weight calculated using nuclear magnetic resonance spectroscopy (NMR method) or mass spectrometry is used. The molecular weight.

In order to increase the mechanical strength of the printing substrate obtained from the resin composition of the present invention, the organic compound (β) has at least one compound having an alicyclic hydrocarbon skeleton or an aromatic hydrocarbon skeleton. In this case, it is preferably 20 wt% or more of the total amount of the organic compound (β), more preferably 50 wt% or more.
When a thermosetting resin composition or a vulcanized rubber material is used as the resin composition of the present invention, a cured resin product is obtained using heat. The method of installing in a high temperature reaction tank, the method of heating directly using an infrared lamp etc. can be mentioned.
When a photosensitive resin composition is used as the resin composition of the present invention, a method of curing the photosensitive resin composition by irradiation with light, that is, ultraviolet rays, visible rays, or electron beams is preferable. When photocuring using ultraviolet rays or visible light, a photopolymerization initiator can be added. The photopolymerization initiator can be selected from those commonly used. For example, photopolymerization of radical polymerization, cationic polymerization, and anionic polymerization exemplified in “Polymer Data Handbook-Basic Edition” edited by the Society of Polymer Science, published in 1986 by Fufukan. A polymerization initiator can be used. As a photopolymerization initiator for inducing a radical polymerization reaction, a hydrogen abstraction type photopolymerization initiator and a decay type photopolymerization initiator are used as particularly effective photopolymerization initiators.

  Although it does not specifically limit as a hydrogen abstraction type photoinitiator, It is preferable to use an aromatic ketone. Aromatic ketone is efficiently converted into an excited triplet state by photoexcitation, and a chemical reaction climate is proposed in which this excited triplet state extracts radicals from surrounding media to generate radicals. The generated radical is considered to be involved in the photocrosslinking reaction. Any compound can be used as the hydrogen abstraction type photopolymerization initiator used in the present invention as long as it is a compound capable of generating hydrogen by extracting hydrogen from the surrounding medium through an excited triplet state. Examples of aromatic ketones include benzophenones, miherer ketones, xanthenes, thioxanthones, and anthraquinones, and it is preferable to use at least one compound selected from these groups.

  Benzophenones refer to benzophenone or derivatives thereof, specifically 3,3 ', 4,4'-benzophenone tetracarboxylic anhydride, 3,3', 4,4'-tetramethoxybenzophenone, and the like. Miherer ketones refer to miherer ketone and its derivatives. Xanthenes refer to derivatives substituted with xanthene and an alkyl group, phenyl group, or halogen group. Thioxanthones refer to thioxanthone and derivatives substituted with an alkyl group, a phenyl group, and a halogen group, and examples thereof include ethylthioxanthone, methylthioxanthone, and chlorothioxanthone. Anthraquinones are anthraquinone and derivatives substituted with an alkyl group, a phenyl group, a halogen group, or the like. The addition amount of the hydrogen abstraction type photopolymerization initiator is preferably 0.1 wt% or more and 10 wt% or less, more preferably 0.5 wt% or more and 5 wt% or less of the total amount of the photosensitive resin composition. When the addition amount is within this range, even when the liquid photosensitive resin composition is cured in the air, the curability of the cured product surface can be sufficiently secured, and light resistance can be secured, which is preferable.

  The decay type photopolymerization initiator refers to a compound in which an active radical is generated by generating a cleavage reaction in the molecule after light absorption, and is not particularly limited. Specific examples include benzoin alkyl ethers, 2,2-dialkoxy-2-phenylacetophenones, acetophenones, acyloxime esters, azo compounds, organic isotope compounds, diketones, and the like. It is preferable to use at least one compound selected from the group consisting of: Examples of benzoin alkyl ethers include benzoin isopropyl ether, benzoin isobutyl ether, and compounds described in “Photosensitive polymer” (Kodansha, 1977, page 228). Examples of 2,2-dialkoxy-2-phenylacetophenones include 2,2-dimethoxy-2-phenylacetophenone and 2,2-diethoxy-2-phenylacetophenone.

  Examples of acetophenones include acetophenone, trichloroacetophenone, 1-hydroxycyclohexylphenylacetophenone, 2,2-diethoxyacetophenone, and the like. Examples of acyl oxime esters include 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime. Examples of the azo compound include azobisisobutyronitrile, diazonium compound, and tetrazene compound. Examples of organic sulfur compounds include aromatic thiols, mono- and disulfides, thiuram sulfides, dithiocarbamates, S-acyl dithiocarbamates, thiosulfonates, sulfoxides, sulfinates, dithiocarbonates, and the like. Examples of diketones include benzyl and methylbenzoyl formate. The addition amount of the collapsible photopolymerization initiator is preferably 0.1 wt% or more and 10 wt% or less, more preferably 0.3 wt% or more and 3 wt% or less of the total amount of the photosensitive resin composition. If the addition amount is within this range, it is preferable because the curability inside the cured product can be sufficiently secured even when the photosensitive resin composition is photocured in the air.

  In particular, in the case of a radical polymerization type photosensitive resin composition to be photocured in an atmosphere having an oxygen concentration of 5 vol% or more, a combination of a hydrogen abstraction type photopolymerization initiator and a decay type photopolymerization initiator as a photopolymerization initiator. Alternatively, it is preferable to use a photopolymerization initiator having both a site functioning as a hydrogen abstraction type photopolymerization initiator and a site functioning as a decay type photopolymerization initiator in the same molecule. In an atmosphere containing 5 vol% or more of oxygen, there is a problem that the curing in the vicinity of the surface is insufficient due to the inhibition of curing by oxygen. Therefore, in order to prevent curing inhibition, special measures such as inert gas atmosphere, underwater atmosphere, or covering the surface of the photosensitive resin composition with a light transmissive film and blocking oxygen are necessary, It is necessary to attach a special mechanism to the exposure apparatus. In particular, when forming a cylindrical photosensitive resin cured product layer, an extremely complicated mechanism is required.

Hydrogen atom in which resin (α) or organic compound (β) is directly bonded to a sulfur atom such as thiol, a compound having a hydrogen atom that is in the α position with respect to an oxygen atom or nitrogen atom present in the molecular chain It is preferable to contain at least 20 wt% or more of the compound having a weight of the total amount of the photosensitive resin composition. More preferably, it is 40 wt% or more. Examples of the atomic group derived from the oxygen atom include alcohols, ethers, esters, and carbonates, and examples of the atomic group derived from the nitrogen atom include urethane, urea, and amide. Although the detailed reaction mechanism is not clear, excitation of the hydrogen abstraction-type photopolymerization initiator is performed by using the hydrogen directly bonded to the α-position hydrogen or sulfur atom existing in the resin (α) or organic compound (β) molecule. This is probably because radical species are generated by the reaction in which the triplet state is efficiently extracted, and the generated radical species contribute to the crosslinking reaction. Many hydrogen abstraction type photopolymerization initiators exhibit strong light absorption in the wavelength range of 200 nm to 300 nm, and these lights are attenuated rapidly inside the photosensitive resin composition layer. It is estimated to be.
In addition, a polymerization inhibitor, an ultraviolet absorber, a dye, a pigment, a lubricant, a surfactant, a plasticizer, a fragrance, and the like can be added to the resin composition of the present invention according to the purpose and purpose.

Inorganic fine particles or inorganic organic composite fine particles can be added to the resin composition of the present invention. In particular, these particles are preferably porous. A porous material is a fine particle with fine pores or fine voids in the particle, and heat is applied to the surface of the cured resin layer in the surface adjustment process, so it occurs in the cutting, grinding, and polishing processes. This is effective in absorbing and removing viscous liquid residue, and also has an anti-tacking effect on the surface.
As a method of molding the resin composition of the present invention into a sheet or cylinder, an existing resin molding method can be used. For example, a doctor blade and a coating method, a die extrusion method, a spray coating method, a gravure coating method, a roll coating method and the like can be exemplified. Moreover, the method etc. which carry out the calendar process of the apply | coated resin composition layer with a roll, and match | combine thickness can be taken. In that case, it is also possible to perform the molding while heating the resin composition within a range that does not deteriorate the performance. In many cases, it is formed on a sheet-like support made of a material such as PET or nickel, but when directly forming on a cylindrical support such as a cylinder of a printing press, a sleeve mounted on an air cylinder, etc. It may be molded on a hollow cylindrical support. The role of the sheet-like support, cylindrical support or hollow cylindrical support is to ensure the dimensional stability of the printing substrate. Therefore, it is necessary to select one having high dimensional stability.

  When evaluated using the linear thermal expansion coefficient, the upper limit value of a preferable material is 100 ppm / ° C. or less, more preferably 70 ppm / ° C. or less. Specific examples of materials include polyester resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polybismaleimide resin, polysulfone resin, polycarbonate resin, polyphenylene ether resin, polyphenylene thioether resin, polyethersulfone resin, all Examples thereof include liquid crystal resins composed of aromatic polyester resins, wholly aromatic polyamide resins, and epoxy resins. Further, these resins can be laminated and used.

  For example, a sheet or the like in which layers of polyethylene terephthalate having a thickness of 50 μm are laminated on both surfaces of a 4.5 μm thick wholly aromatic polyamide film may be used. In addition, a porous sheet, for example, a cloth formed by knitting fibers, a nonwoven fabric, a film in which pores are formed, or the like can be used as a back film. When a porous sheet is used as the back film, the photosensitive resin cured product layer is integrated with the back film by photocuring after impregnating the photosensitive resin composition into the pores, so that high adhesion is obtained. be able to. The fibers forming the cloth or nonwoven fabric include glass fibers, alumina fibers, carbon fibers, alumina / silica fibers, boron fibers, high silicon fibers, potassium titanate fibers, sapphire fibers, and other natural fibers, such as cotton and linen. Examples thereof include semi-synthetic fibers such as fibers, rayon and acetate, and synthetic fibers such as nylon, polyester, acrylic, vinylon, polyvinyl chloride, polyolefin, polyurethane, polyimide, and aramid. Further, cellulose produced by bacteria is a highly crystalline nanofiber, and is a material capable of producing a thin nonwoven fabric with high dimensional stability.

  Examples of a method for reducing the linear thermal expansion coefficient of the support include a method of adding a filler, a method of impregnating or coating a resin on a mesh cloth such as wholly aromatic polyamide, a glass cloth, or the like. As the filler, generally used organic fine particles, inorganic fine particles such as metal oxide or metal, organic / inorganic composite fine particles, and the like can be used. In addition, porous fine particles, fine particles having cavities inside, microcapsule particles, and layered compound particles in which a low molecular compound intercalates can be used. In particular, metal oxide fine particles such as alumina, silica, titanium oxide, and zeolite, latex fine particles made of polystyrene / polybutadiene copolymer, natural product-based organic fine particles such as highly crystalline cellulose, and the like are useful.

By performing physical and chemical treatment on the surface of the sheet-like support, cylindrical support, or hollow cylindrical support used in the present invention, the adhesion with the photosensitive resin composition layer or the adhesive layer is improved. Can be made. Examples of the physical treatment method include a sand blast method, a wet blast method for injecting a liquid containing fine particles, a corona discharge treatment method, a plasma treatment method, an ultraviolet ray or vacuum ultraviolet ray irradiation method, and the like. The chemical treatment method includes a strong acid / strong alkali treatment method, an oxidant treatment method, a coupling agent treatment method, and the like.
The molded photosensitive resin composition layer is cured by light irradiation to form a cured photosensitive resin layer. It can also be cured by light irradiation while molding. Examples of the light source used for curing include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a germicidal lamp, a carbon arc lamp, a xenon lamp, and a metal halide lamp. The light applied to the photosensitive resin composition layer preferably has a wavelength of 200 nm to 300 nm. In particular, since many hydrogen abstraction type photopolymerization initiators have strong light absorption in this wavelength region, when having light with a wavelength of 200 nm to 300 nm, sufficient curability of the surface of the cured photosensitive resin layer is ensured. be able to. Although the light source used for curing may be one type, the curability of the resin may be improved by curing using two or more types of light sources having different wavelengths, so two or more types of light sources may be used. There is no problem.

In this invention, the cushion layer which consists of elastomers can also be formed in the lower part of the resin cured material layer in which a concave pattern is formed. In general, since the thickness of the layer to be laser engraved is 0.1 to several mm, the other lower layers may be made of materials having different compositions. The cushion layer is preferably an elastomer layer having a Shore A hardness of 10 to 70 degrees. When the Shore A hardness is 10 degrees or more, the print quality can be ensured because the film is appropriately deformed. Moreover, if it is 70 degrees or less, it can play the role as a cushion layer.
The cushion layer is not particularly limited, and any cushion layer may be used as long as it has rubber elasticity, such as a thermoplastic elastomer, a photocurable elastomer, and a thermosetting elastomer. It may be a porous elastomer layer having fine pores. In particular, from the viewpoint of processability to a sheet-like or cylindrical printing plate, it is simple and preferable to use a liquid photosensitive resin composition that is cured by light and to use a material that becomes an elastomer after curing.

Specific examples of the thermoplastic elastomer used for the cushion layer include SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), SEBS (polystyrene-polyethylene / polybutylene-polystyrene), which are styrenic thermoplastic elastomers, and the like. Olefin-based thermoplastic elastomer, urethane-based thermoplastic elastomer, ester-based thermoplastic elastomer, amide-based thermoplastic elastomer, silicon-based thermoplastic elastomer, fluorine-based thermoplastic elastomer, and the like.
Examples of the photocurable elastomer include those obtained by mixing a photopolymerizable monomer, a plasticizer, a photopolymerization initiator, and the like with the thermoplastic elastomer, and a liquid composition obtained by mixing a photopolymerizable monomer, a photopolymerization initiator, etc. with a plastomer resin. Can be mentioned. In the present invention, unlike the design concept of the photosensitive resin composition, in which the function of forming a fine pattern is an important element, it is not necessary to form a fine pattern using light, and by curing by overall exposure, Since it is sufficient to ensure a certain level of mechanical strength, the degree of freedom in selecting a material is extremely high.
Moreover, non-sulfur cross-linked rubbers such as sulfur cross-linked rubber, organic peroxide, phenol resin initial condensate, quinone dioxime, metal oxide, and thiourea can also be used.
Furthermore, it is also possible to use a three-dimensionally crosslinked elastomer obtained by using a curing agent that reacts with a telechelic liquid rubber.

[Printing substrate]
The printing substrate obtained by the above production method has high plate thickness accuracy, and is preferably used for applying a liquid electronic material or optical material.
As a printing substrate manufactured using the manufacturing method of the present invention, a cylindrical printing substrate formed on a cylindrical support such as a cylinder or a hollow cylindrical support such as a sleeve, or a sheet-like support The sheet-like printing base material formed in this can be mentioned. In order to manufacture a hollow cylindrical printing substrate, an air cylinder is used as a cylindrical support, and a metal or fiber reinforced plastic sleeve as a hollow cylindrical support is mounted on the cylindrical support. Is preferred.

By forming the modified layer on the surface of the printing substrate of the present invention, it is possible to reduce the tack of the printing plate surface and improve the wettability to the electronic material or optical material. Examples of the modified layer include a film treated with a compound that reacts with a surface hydroxyl group such as a silane coupling agent or a titanium coupling agent.
A widely used silane coupling agent is a compound having in its molecule a functional group highly reactive with the surface hydroxyl group of the substrate. Examples of such a functional group include a trimethoxysilyl group and a triethoxysilyl group. Group, trichlorosilyl group, diethoxysilyl group, dimethoxysilyl group, dimonochlorosilyl group, monoethoxysilyl group, monomethoxysilyl group, monochlorosilyl group. Further, at least one of these functional groups exists in the molecule, and is immobilized on the surface of the base material by reacting with the surface hydroxyl group of the base material. Further, the compound constituting the silane coupling agent of the present invention is selected from acryloyl group, methacryloyl group, active hydrogen-containing amino group, epoxy group, vinyl group, perfluoroalkyl group, and mercapto group as reactive functional groups in the molecule. Those having at least one functional group or those having a long-chain alkyl group can be used.

  Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (di-tridecyl phosphite) titanate, Tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (octylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyl Dimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate Over DOO, isopropyl tri (dioctyl sulfate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) may include compounds such as titanates.

When the coupling agent molecule immobilized on the surface has a polymerizable reactive group in particular, it can be formed into a stronger film by irradiating with light, heat, or electron beam and crosslinking after immobilization on the surface. .
In the present invention, the above-described coupling agent is diluted with water-alcohol or acetic acid water-alcohol mixed solution as necessary. The concentration of the coupling agent in the treatment liquid is preferably 0.05 to 10.0% by weight.
The coupling agent treatment method in the present invention will be described. The treatment liquid containing the coupling agent is applied to the surface of the produced printing substrate. The method for applying the coupling agent treatment liquid is not particularly limited, and for example, an immersion method, a spray method, a roll coating method, or a brush coating method can be applied. Further, the coating treatment temperature and the coating treatment time are not particularly limited, but are preferably 5 to 60 ° C., and the treatment time is preferably 0.1 to 60 seconds. Furthermore, it is preferable to dry the treatment liquid layer on the surface of the resin plate under heating, and the heating temperature is preferably 50 to 150 ° C.

Before treating the printing plate surface with a coupling agent, a method of irradiating light in a vacuum ultraviolet region having a wavelength of 200 nm or less such as a xenon excimer lamp, or exposure to a high energy atmosphere such as plasma, a hydroxyl group on the printing plate surface. And the coupling agent can be immobilized at a high density.
Also, when the layer containing inorganic porous particles or organic / inorganic composite porous particles is exposed on the printing plate surface, it is treated in a high energy atmosphere such as plasma, and the organic layer on the surface is slightly etched away. As a result, minute irregularities can be formed on the surface of the printing plate. By this treatment, the effect of improving the ink wettability can be expected by reducing the tack of the printing plate surface and making the inorganic porous particles exposed on the surface easy to absorb the ink.
In the printing base material of this invention, after forming a concave pattern, you may pass through the process of irradiating the surface of the obtained printing base material with an ultraviolet-ray, and removing the stickiness of the surface. Examples of the atmosphere for irradiating with ultraviolet rays include air, an inert gas atmosphere, and water. It is also a preferable method to treat the surface of the printing substrate with a treatment liquid containing a photopolymerization initiator before the ultraviolet irradiation.

[Reproduction method of printing substrate]
When the printing substrate is used for a long period of time in the printing process and used very frequently, the surface may be slightly worn, and the surface roughness may change from the initial level. Even in such a case, it is possible to regenerate the printing substrate by fixing the printing substrate on the cylindrical support again and adjusting the surface using a technique such as cutting, grinding, or polishing. As a suitable example of such a method, for example, after mounting the printing substrate used in the printing process on a cylindrical support, the printing support is rotated while rotating the cylindrical support in the circumferential direction. There is a method for regenerating a printing substrate characterized by adjusting the surface of the material again.

[Method of manufacturing electronic material or optical material]
The printing substrate obtained by the production method of the present invention is particularly suitable as a printing substrate for applying a liquid electronic material or optical material.
Next, the manufacturing method of an electronic member or an optical member is explained in full detail.
The manufacturing method of an electronic member or an optical member includes a step of attaching the printing substrate obtained by the above method to a cylindrical printing cylinder of a printing machine, a liquid electronic material or an optical material attached to the surface of the printing substrate, It is preferable to include a step of transferring onto the printing substrate and a step of fixing the electronic material or optical material onto the substrate to be printed.
In a method of applying an electronic material or an optical material on a substrate to be printed by a printing method, as a method of forming the electronic material or the optical material on the substrate to be printed, in particular, the printing pressure on the substrate to be printed is low, The flexographic printing method is particularly preferable because only the convex portion where the electronic material or the optical material adheres to the surface of the substrate to be printed comes into contact with the substrate to be printed.

  In the resin relief printing plate used in the flexographic printing method, when a convex pattern having an outermost surface dimension of 200 μm square and a height of 500 μm is formed, the height difference between the central portion and the edge portion of the convex pattern may be 30 μm or less. preferable. If the height difference between the central portion and the edge portion of the convex pattern is 30 μm or less, printing can be performed with a low printing pressure, and the printed film thickness becomes uniform. The present invention can easily solve the cupping phenomenon, that is, the phenomenon in which the film thickness at the central portion of the pattern becomes thin due to photocuring shrinkage, which has been a problem in the photosensitive resin plate formed using the conventional photoengraving technology. The purpose of the present invention is to adjust the surface of the cured resin layer once cured over the entire surface using a technique such as cutting, grinding, polishing, etc., and then form a concave pattern on the adjusted surface.

The electronic material formed by applying the electronic material of the present invention refers to an electronic material formed by patterning at least one selected from an insulator, a semiconductor, and a conductor. Although not particularly limited, specifically, a conductor pattern for forming a coil, antenna, electrode, wiring, etc., a dielectric such as a capacitor, an interlayer insulating film, an insulating pattern for forming an alignment film for a liquid crystal display, etc. And organic semiconductor patterns for forming a light emitting layer, a charge transfer layer, a charge injection layer, and the like of a transistor, a diode, and an organic electroluminescence element. The insulator includes a resist material such as a process resist and a permanent resist. Examples of the optical member formed by applying an optical material include thin film optical components such as an antireflection film, a filter film, a polarizing film, and a light guide plate. The filter film includes a color filter and a black matrix used in a flat panel display or the like.
The solvent contained in the electronic material or optical material is determined by the solubility of the non-volatile components in these materials and the drying property in the printing process, but it is an aromatic hydrocarbon compound, nitrogen-containing hydrocarbon compound, ester. It is preferable that at least one compound selected from a compound, an amide compound, a glycol monoether compound, and a halogen-containing hydrocarbon compound is contained in an amount of 20 wt% or more of the total amount of the solvent.

  In the printing substrate of the present invention, a cured photosensitive resin having resistance to a solvent contained in the electronic material or optical material to be used can be designed. In the electronic material or optical material for forming the electronic member or optical member of the present invention, as a solvent for dissolving or dispersing the functional compound, ethyl acetate, propyl acetate, butyl acetate, methyl benzoate, ethyl benzoate, γ- Ester compounds such as butyl lactone, amide compounds such as γ-butyl lactam, ether compounds such as tetrahydrofuran, oxirane, dibutyl ether, glycol monoether compounds such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, hexane, heptane, octane, Hydrocarbon compounds such as toluene and xylene, halogen-containing hydrocarbon compounds such as chloroform, dichloroethane, tetrachloroethylene, chlorobenzene and dichlorobenzene, nitrogen-containing hydrocarbon compounds such as methylpyrrolidone and pyridine Etc. The solvent resistance to the solvent contained in the electronic material or optical material of the printing substrate of the present invention is evaluated by a solvent immersion swelling test, and the weight change rate before and after immersion in the solvent is 10 wt% or less. preferable. More preferably, it is 5 wt% or less. The solvent immersion swelling test in the present invention is performed by immersing a test sample in a solvent at room temperature for 24 hours. When the weight change rate is 10 wt% or less, the dimensional change of the printing substrate is small, a fine pattern can be printed, and a thin film can be uniformly applied.

  As a guideline for designing a material for a printing substrate having high solvent resistance, it is preferable to select a material having a large difference in solubility parameter between the main portion constituting the resin (α) to be used and the solvent. The solubility parameter (hereinafter, abbreviated as SP) is also called a solubility factor, and is an index indicating the polarity of a substance and is an index of affinity. The solubility parameter is also described in the Dictionary of Chemistry (Tokyo Chemical Dojinsha, published in 1989). In general, the closer the SP values of the two, the easier it is to melt together, and when one is solid, it is easy to get wet, and it is used as one standard for selecting an adhesive or a solvent. In the present invention, since it is necessary to have resistance to the solvent contained in the electronic material or optical material to be used, there is a difference in solubility parameter between the main part constituting the resin (α) to be used and the solvent. It is preferable to select a larger one.

  For example, for hydrocarbon compounds such as hexane, heptane, octane, cyclohexane, kerosene, linseed oil, soybean oil, toluene, xylene, etc., rather than selecting a prepolymer having a hydrocarbon-based polybutadiene skeleton or polyisoprene skeleton. Unsaturated polyester, polyester polyol, unsaturated polyurethane using polycarbonate diol, and the like are preferable. In addition, for nitrogen-containing hydrocarbon compounds such as methylpyrrolidone, pyridine, acetonitrile, dimethylformamide, ketones such as acetone and methyl ethyl ketone, and polyalkylene skeletons such as polybutadiene rather than selecting polyester and polyurethane. Prepolymers having are preferred. For butoxyethanol and ethoxyethanol, unsaturated polyurethane and polymers having a polyalkylene skeleton are preferred. Unsaturated polyesters are preferred for halogenated aromatic hydrocarbon compounds such as chlorobenzene and dichlorobenzene. For ester compounds such as benzoic acid esters, ethyl acetate, propyl acetate, and butyl acetate, unsaturated polyesters and unsaturated polyurethanes having a polycarbonate diol as a skeleton are preferable.

The substrate to be printed for printing the electronic material or the optical material used in the present invention is preferably at least one substrate selected from a glass plate, a ceramic plate, a film, a metal plate, a metal sheet, and paper. . Examples of films include plastic films and metal films, plastic films and metal films laminated with different materials such as plastic films with ceramics and metal thin films formed on the surface, and paper includes fibers Anything may be used as long as it is formed from a shape. It may be a woven fabric or a non-woven fabric. Examples of the fibrous material include natural fibers, synthetic fibers, glass fibers, ceramic fibers, and metal fibers. Further, the glass plate may have a surface coated with a thin film of an electrode material such as ITO or zinc oxide.
The thickness of the print pattern that can be printed on the substrate to be printed in the printing method of the present invention is preferably 1 nm or more and 10 μm or less after the solvent component in the electronic material or the optical material is removed by drying. More preferably, they are 5 nm or more and 5 micrometers or less, More preferably, they are 10 nm or more and 1 micrometers or less. When the film thickness is 1 nm or more, the functions of an insulator, a semiconductor, and a conductor can be expressed. When the film thickness is 10 μm or less, the solvent component in the electronic material or the optical material can be easily removed.

  The printing machine used when applying the electronic material or optical material on the substrate to be printed using the printing substrate of the present invention to produce the electronic member or optical member is of a type that can be printed using a resin relief plate. If it is a printing machine, it will not specifically limit, A commercially available flexographic printing machine, a dry offset printing machine, a liquid crystal aligning film printing machine etc. can be mentioned. A film for printing in a roll-to-roll form, a printing machine for printing on paper, etc., and a printing machine for printing on a sheet-like substrate to be printed are commercially available. Further, it may be a printing machine that uses a sheet-like printing substrate wound around a plate cylinder, or a sleeve-compatible printing machine that uses a hollow cylindrical printing substrate mounted on an air cylinder. The film thickness of the electronic material or optical material formed on the substrate to be printed includes the roughness of the surface of the printing substrate, the viscosity of the electronic material or optical material and the concentration of non-volatile components, the cell on the anilox roll surface of the printing press. It depends on factors such as density and cell capacity. By combining these factors, the degree of freedom in controlling the film thickness is high. It is possible to mold from an ultra-thin film of about 10 nm to a thin film of about 10 μm.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not restrict | limited by these.
(1) Measurement of number average molecular weight The number average molecular weight of resin ((alpha)) was calculated | required by converting into polystyrene with known molecular weight using the gel permeation chromatograph method (GPC method). Using a high-speed GPC device “HLC-8020” (trademark, manufactured by Tosoh Corporation, Japan) and a polystyrene packed column “TSKgel GMHXL” (trademark, manufactured by Tosoh Corporation, Japan), the measurement was performed with tetrahydrofuran (THF). The column temperature was set to 40 ° C. As a sample to be injected into the GPC apparatus, a THF solution having a resin concentration of 1 wt% was prepared to have an injection amount of 10 μl. As a detector, an ultraviolet absorption detector was used. The resin (α) used in the examples or comparative examples of the present invention had a polydispersity (Mw / Mn) determined by the GPC method greater than 1.1. Therefore, the number average molecular weight Mn determined by the GPC method was Adopted.

[Example 1]
(Manufacture of resin (α))
In a 1 L separable flask equipped with a thermometer and a stirrer, 51 parts by weight of polyoxyethylene (EO) -polyoxypropylene (PO) block copolymer diol having a number average molecular weight of 2500 (EO / PO molar ratio 1/4) , 33.9 parts by weight of poly (3-methyl-1,5-pentanediol adipate) having a number average molecular weight of 3000, 0.003 parts by weight of dibutyltin tin dilaurate as a catalyst, and 2,6-di-tert-butyl-4-methylphenol 0.1 part by weight was added and stirred and mixed. The water content in the system was adjusted to 400 ppm. Next, 6 parts by weight of tolylene diisocyanate was added dropwise with stirring at an external temperature of 40 ° C., and then the external sound was gradually raised and reacted at 80 ° C. for 5 hours. Furthermore, 4 parts by weight of 2-hydroxypropyl methacrylate was added and reacted for 2 hours to obtain an unsaturated polyurethane. The number average molecular weight in terms of polystyrene by GPC was 22500.

(Adjustment of photosensitive resin composition)
For 65 parts by weight of the unsaturated polyurethane produced as described above, 13 parts by weight of diethylene glycol-2-ethylhexyl ether acrylate, 20 parts by weight of diethylene glycol monobutyl ether monomethacrylate, 2 parts by weight of trimethylolpropane trimethacrylate as the organic compound (β), As photopolymerization initiator, 2,2-dimethoxy-2-phenylacetophenone 0.6 parts by weight, benzophenone 1 part by weight, and as an additive, an inorganic porous material “Pyrospher C-1504” (trademark, manufactured by Fuji Sicilian Chemical Co., Ltd., Porous fine powder silica, number average particle diameter 4.5 μm, specific surface area 520 m ² / g, average pore diameter 12 nm, pore volume 1.5 ml / g, ignition loss 2.5 wt%, oil absorption 290 ml / 100 g), 2,6-di-tert-butyl as a polymerization inhibitor 4-methylphenol 0.05 parts by weight were mixed to give a photosensitive resin composition A.

(Preparation of sheet-shaped photosensitive resin cured product)
A double-sided adhesive tape having a width of 10 mm and a thickness of 50 μm was attached in the major axis direction of a cylinder having a width of 1 m and a diameter of 318.47 mm. A PET film having a thickness of 180 μm was wound around the surface of a cylinder, which is a cylindrical support, and the positions were aligned and fixed so that both ends of the PET film came to the double-sided adhesive tape.
The adjusted photosensitive resin composition is formed on a PET film into a sheet having a thickness of 2.8 mm, and the metal halide stamp “M056-L21” (trade name, manufactured by Eye Graphics Co., Ltd.) is removed while rotating the cylinder. The incoming light was irradiated from the surface where the photosensitive resin layer was exposed in the atmosphere to obtain a photocured product. The amount of energy irradiated was 4000 mJ / cm ² (a value obtained by integrating the illuminance measured with the UV-35-APR filter over time). The lamp illuminance on the irradiated surface was measured using a UV meter “UV-M02” (trade name, manufactured by Oak Manufacturing Co., Ltd.). The lamp illuminance measured using the UV-35-APR filter was 100 mW / cm ² , and the lamp illuminance measured using the UV-25-filter was 14 mW / cm ² .
The surface of the obtained photocured product was cut with a cutting tool while rotating the cylinder, and then ground while rotating the cylinder and a carborundum grinding wheel, and the surface was polished using a 1000th sandpaper.
The time required from the step of winding the PET film around the surface of the cylindrical support to the polishing step was about 20 minutes.
The thickness of the obtained photocured product was uniform, and the thickness accuracy including the PET film was 2.8 mm ± 10 μm. The thickness was measured at intervals of 3 cm using an apparatus “Digimatic Indicator ID-C112” (trade name, manufactured by Mitutoyo Corporation) capable of measuring up to 1 μm.

(Preparation of sheet-like printing substrate)
A band-shaped concave pattern having a width of 20 mm and a depth of 1 mm was formed on the surface of the photocured product obtained as described above using a cutting tool at intervals of 30 cm by a cutting method while rotating the cylinder. Furthermore, while fixing the cylinder and rotating a grinding wheel having a width of 20 mm, a concave pattern having a depth of 1 mm was formed at intervals of 20 cm while moving in the longitudinal direction of the cylinder. The figure which looked at the formed pattern from the upper part of the sheet-like printing base material was shown to FIG. 2 (A).
Furthermore, the photocured material layer was cut using a cutter at the joints at both ends of the PET film used as the sheet-like support, and the sheet-like printing substrate 1 was peeled off from the cylinder.
The time required to form the concave pattern on the surface of the photocured product was about 10 minutes.

(Print evaluation)
Printing evaluation was carried out using the sheet-like printing substrate 1 obtained as described above and a liquid crystal alignment film printer. Viscosity of conductive ink “silver nanopaste” (trade name, manufactured by Harima Kasei Co., Ltd., solvent tetradecane, solvent content 30 wt%) in which ultrafine particles of silver (average particle diameter 7 nm) are dispersed on the surface of the glass substrate to be cleaned Were used by adjusting with solvent components, and printing, drying, and firing (temperature 150 ° C.) were performed so that the film thickness of the ink after firing was 1 μm. A convex pattern of 18 cm × 28 cm was formed on the sheet-like printing substrate, and a solid pattern of that dimension was uniformly formed on the glass surface. The film thickness after firing was 1 μm and uniform.

(Measurement of swelling rate)
The test sample was applied to the photosensitive resin composition 10 mm × 50 mm in a thickness of 1 mm, and irradiated with energy of 1800 mJ / cm ² using a flexo sales machine “ALF plate making machine” (trademark, manufactured by Asahi Kasei Chemicals). To cure and adjust.
By immersing the prepared test sample in tetradecane, which is a dilution solvent of the above “silver nanopaste” (trade name), at 20 ° C. for 24 hours, wiping off droplets adhering to the surface, and measuring the amount of weight increase The swelling rate was determined. As a result, the swelling rate was 3.0%.

[Example 2]
(Manufacture of resin (α))
In a 2 L separable flask equipped with a thermometer and a stirrer, 212 parts by weight of diethylene glycol, 152 parts by weight of propylene glycol, 90 parts by weight of 1,4-butanediol, 511 parts by weight of adipic acid, 87 parts by weight of fumaric acid, tetrahydrophthalic anhydride 127 parts by weight and 1.2 parts by weight of p-methoxyphenol were reacted in a nitrogen atmosphere at normal pressure and 230 ° C. for 4 hours, and then further reacted under reduced pressure of 100 mmHg for 4 hours to obtain an unsaturated polyester having an acid value of 23. .
560 parts by weight of this unsaturated polyester, 33.6 parts by weight of hexamethylene diisocyanate and 0.6 part by weight of 2,6-di-tert-butyl-4-methylphenol were mixed and reacted at 80 ° C. for 4 hours. Then, 43.2 parts by weight of hydroxypropyl methacrylate and 0.2 parts by weight of dibutyltin tin dilaurate were added, and the mixture was further reacted at 80 ° C. for 2 hours to obtain unsaturated polyester urethane. The polystyrene equivalent number average molecular weight of this product by GPC was 7000.

(Adjustment of photosensitive resin composition)
With respect to 66.8 parts by weight of the unsaturated polyester urethane produced as described above, 16.63 parts by weight of diethylene glycol dimethacrylate, 8.28 parts by weight of diacetone acrylamide, and 8.28 parts by weight of diethylene glycol dimethacrylate as the organic compound (β). In addition, 0.6 part by weight of 2,2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator and 1 part by weight of benzophenone as an additive, an inorganic porous material “Pyrospher C-1504” (manufactured by Fuji Sicilian Chemical Co., Ltd., porous Fine powder silica, trademark, number average particle diameter 4.5 μm, specific surface area 520 m ² / g, average pore diameter 12 nm, pore volume 1.5 ml / g, loss on ignition 2.5 wt%, oil absorption 290 ml / 100 g) 5 parts by weight, 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor 0 05 parts by weight were mixed to obtain a photosensitive resin composition b.

(Formation of sheet-shaped photosensitive resin cured product)
A sheet-like printing substrate was prepared in the same manner as in Example 1 except that the photosensitive resin composition i was used.
The thickness of the obtained sheet-like printing substrate was uniform, and the accuracy was 2.8 mm ± 10 μm. The measurement was performed by the method described in Example 1.

(Preparation of sheet-like printing substrate)
A concave pattern was formed in the obtained sheet-shaped photosensitive resin cured product in the same manner as in Example 1, and the sheet-shaped printing substrate 2 was obtained by peeling off from the cylinder.

(Print evaluation)
Using the sheet-like printing substrate 2 obtained as described above, the printing evaluation of the organic high EL light emitting layer was performed using the same printing machine as in Example 1. As a substrate to be printed, an ITO film (anode) having a thickness of 0.1 μm is formed on the surface of a 0.7 mm thick glass substrate (soda lime glass) by a vacuum deposition method, and then UV-ozone cleaning is performed. After removing the deposits such as organic matter, the coating liquid “Baytron P” (trademark, polyethylene dioxythiophene) containing polyethylene dioxythiophene as a hole transport material by spin coating on the surface of the ITO film side of the equipment. Polystyrene sulfonate (PEDT / PSS, manufactured by Bayer) was applied and dried at 70 to 80 ° C. to prepare a hole transport layer. Poly (9,9-dialkylfluorene (PDAF)) is used as the organic polymer light-emitting body, and it is dissolved in a solvent (xylene) so that the solid content concentration is 2 wt%. Used and printed. As a result, the thickness of the ink printed on the hole transport layer (before drying) was 6 μm, and the thickness of the light emitting layer after drying at 80 ° C. for 30 minutes was 0.12 μm and uniform.

(Measurement of swelling rate)
The test sample was coated with the photosensitive resin composition A 10 mm × 50 mm in a thickness of 1 mm, and irradiated with energy of 1800 mJ / cm ² using a flexo sales machine “ALF plate making machine” (trademark, manufactured by Asahi Kasei Chemicals). To cure and adjust.
The prepared test sample is immersed in xylene, which is the solvent of the ink for forming the light emitting layer, at 20 ° C. for 24 hours, and then the droplet adhering to the surface is wiped off, and the weight increase is measured to determine the swelling rate. It was. As a result, the swelling rate was 1.1%.

[Example 3]
(Manufacture of resin (α))
In a 1 L separable flask equipped with a thermometer and a stirrer, 100 parts by weight of polycarbonate diol “PCDL L4672” (trademark, manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight 1990, OH value 56.4) and tolylene diisocyanate 6.9 After adding parts by weight, the mixture was allowed to react at 80 ° C. for 3 hours, and then 3.3 parts by weight of 2-methacryloyloxyisocyanate was added, followed by further reaction for 3 hours to obtain an unsaturated polyurethane. The polystyrene-reduced number average molecular weight of this product by GPC was about 10,000.

(Adjustment of photosensitive resin composition)
With respect to 100 parts by weight of the unsaturated polyurethane produced as described above, 25 parts by weight of benzyl methacrylate, 19 parts by weight of cyclomethacrylate, 6 parts by weight of butoxydiethylene glycol methacrylate as an organic compound (β), and 2,2-dimethoxy as a photopolymerization initiator 0.6 parts by weight of 2-phenylacetophenone, 1 part by weight of benzophenone, and inorganic porous material “Phosphorus C-1504” (manufactured by Fuji Sicilian Chemical Co., Ltd., porous fine powder silica, trademark, number average particle) 4.5 μm diameter, specific surface area 520 m ² / g, average pore diameter 12 nm, pore volume 1.5 ml / g, ignition loss 2.5 wt%, oil absorption 290 ml / 100 g) 5 parts by weight, 2,6 as a polymerization inhibitor -Mixing 0.05 parts by weight of di-t-butyl-4-methylphenol, photosensitive resin composition It was obtained.

(Preparation of sheet-like printing substrate)
A sheet-like printing substrate 3 was produced in the same manner as in Example 1 except that the photosensitive resin composition was used. The thickness of the obtained sheet-like printing substrate was uniform, and the accuracy was 2.8 mm ± 10 μm. The measurement was performed by the method described in Example 1.

(Print evaluation)
Printing evaluation was performed in the same manner as in Example 1 except that the sheet-like printing substrate 3 was used. As a result, the film thickness after firing was 1 μm and uniform.

(Measurement of swelling rate)
The test sample was coated with the photosensitive resin composition 10 mm × 50 mm in a thickness of 1 mm, and irradiated with 1800 mJ / cm ² of energy using a flexo sales machine “ALF plate making machine” (trademark, manufactured by Asahi Kasei Chemicals). To cure and adjust.
By immersing the prepared test sample in tetradecane, which is a dilution solvent of the above “silver nanopaste” (trade name), at 20 ° C. for 24 hours, wiping off droplets adhering to the surface, and measuring the amount of weight increase The swelling rate was determined. As a result, the swelling rate was 0.9%.

[Comparative Example 1]
(Preparation of photosensitive resin plate)
Using the same photosensitive resin composition as in Example 1, an adhesive having a thickness of several micrometers is applied to one side of a PET film having dimensions of 1100 mm × 1000 mm and a thickness of 180 μm on the glass surface of a plate making machine for flexographic plates. The photosensitive resin plate base film was placed so that the surface on which the adhesive layer was applied faced up, and was brought into vacuum contact. On the base film, the photosensitive resin composition is molded and spread using a carriage and a transparent cover film having a thickness of 100 μm with a thickness set to 2.62 mm in an area of 1000 mm × 900 mm. did. The carriage is a traveling molding and spreading device having a laminate roller, a bucket (resin reservoir), a film, a guide, and the like, and a spacer along the glass surface (a rail that moves up and down to regulate the thickness of the plate). This is an apparatus for casting (coating) the photosensitive resin composition layer to a predetermined thickness while casting the photosensitive resin composition while running on top and feeding the film.
Next, the photosensitive resin composition was cured by irradiating ultraviolet rays from the upper part of the obtained laminate with an exposure device provided in the plate making machine. After completion of exposure, the cover film was peeled off to obtain a cured photosensitive resin. When the thicknesses of the PET base film and the cured photosensitive resin were measured, the accuracy was 2.8 mm ± 50 μm, which was not uniform as compared with Example 1. The measurement was performed by the method described in Example 1.

(Laser engraving)
A concave pattern similar to that of Example 1 was engraved on the surface of the obtained cured cured photosensitive resin using a carbon dioxide laser engraving machine “ZED-mini-1000” (trademark, manufactured by ZED). One laser beam of the laser engraving machine used for laser engraving was condensed to a diameter of about 25 μm, and the average output of the laser was 250 W. The time required to complete the laser engraving was 3 hours.

(Print evaluation)
Printing evaluation was performed in the same manner as in Example 1. As a result, in the solid pattern of 280 mm × 180 mm formed on the glass surface, the non-uniformity was inferior to that of Example 1, interference fringes were observed, and unevenness was conspicuous.

[Comparative Example 2]
(Preparation of photosensitive resin plate)
For the photosensitive resin plate, the same photosensitive resin composition as in Example 1 is used, and an adhesive having a thickness of several μm is applied to one side of a 180 μm thick PET film on the glass surface of a flexographic plate making machine. The base film was placed so that the surface on which the adhesive layer was applied was facing up, and was brought into vacuum contact. On the base film, the photosensitive resin composition A was molded and spread using a carriage having a thickness of 2.62 mm and a negative film for forming a convex pattern. The carriage is a traveling molding and spreading device having a laminate roller, a bucket (resin reservoir), a negative film, a guide, and the like. A spacer along the glass surface (a rail that moves up and down to regulate the thickness of the plate) ) A device that casts the photosensitive resin composition to a predetermined thickness while casting the photosensitive resin composition while running on top and feeding a negative film. On the negative film, a pattern in which opening patterns of 280 mm × 180 mm were regularly arranged was formed as in Example 1.

  Next, an ultraviolet ray is first irradiated from the upper part of the obtained laminate by an exposure device provided at the lower part of the plate making machine, the entire part is exposed to the base, and the light source provided at the upper part is passed through the negative film. The photosensitive resin composition a was hardened by exposing. After the exposure was completed, the negative film was peeled off, and the uncured portion that was not irradiated with ultraviolet rays was scraped off and collected, and then the uncured portion was completely removed with a weak alkaline detergent. Furthermore, ultraviolet rays were irradiated in water to completely cure the resin plate, and then water was removed using a hot air dryer to obtain a sheet-like printing substrate. That is, a sheet-like printing substrate having a plate thickness of 2.8 mm and a concave pattern depth of 1 mm was obtained. The central portion of the solid pattern of 280 mm × 180 mm of this sheet-like printing substrate was lower than the peripheral portion, and the height difference was about 50 μm. The measurement was performed with a trade name “System Electric Biological Microscope BX-61” (manufactured by Olympus Optical Co., Ltd.).

(Print evaluation)
Printing evaluation was performed in the same manner as in Example 1 except that the sheet-like printing substrate obtained as described above was used. As a result, the solid pattern of 280 mm × 180 mm was in a state where only the outer peripheral portion of the solid pattern was printed and the central portion was not printed under a low printing pressure condition. Even in printing under conditions where the printing pressure was set high, the end of the solid pattern was thick and the center was thin.

  The present invention relates to a method for producing a printing substrate used in the production of an electronic member or an optical member, and more specifically, an electronic material for forming an electronic member or an optical material for forming an optical member on a substrate to be printed. It is suitable as a method for producing a printing substrate for application, a method for producing an electronic component or an optical member, and a method for regenerating a printing substrate. The printing substrate obtained by the present invention is a conductor, semiconductor, insulator pattern formation, resist material pattern formation, antireflection film for optical components, color filter, pattern formation of functional materials such as (near) infrared cut filter, Is suitable for forming a coating film / pattern of an alignment film, a base layer, a light emitting layer, an electron transport layer, and a sealing material layer in the production of a display element such as a liquid crystal display or an organic electroluminescence display.

It is the schematic which shows an example of the cylindrical support body used by this invention. (A) is the schematic which looked at the pattern of the sheet-like printing base material from the top by this invention. (B) is sectional drawing at the time of cut | disconnecting the sheet-like printing base material of this invention by the line C. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Cylindrical support body surface 2 Long axis of cylindrical support body 3 Space | gap of concave pattern 4 Width of concave pattern 5 Depth of concave pattern 6 Thickness of sheet-like printing substrate

Claims (13)

(A) a step of forming a cured resin layer on the surface of the cylindrical support, (b) at least one method selected from cutting, grinding, and polishing on the surface of the obtained cured resin layer. A step of adjusting the thickness and roughness of the cured resin layer , and (c) a concave pattern formed on the surface of the formed cured resin layer , in the major axis direction and the circumferential direction of the cylindrical support. A concave pattern forming step for forming a groove-shaped concave pattern , which exists between the patterns of convex portions which are print patterns to be arranged ;
Including
A method of forming a concave pattern of the step (c), the cutting, at least one method selected Grinding or al, the groove-shaped concave patterns while rotating the cylindrical support in the circumferential direction And a step of fixing the cylindrical support and forming a groove-shaped concave pattern in the longitudinal direction of the cylindrical support, and the groove-shaped concave pattern has a width of 0.05 mm or more and 50 mm. hereinafter, a method of manufacturing a printed substrate, which is a less straight linear pattern 20mm or more depth 0.05 mm. The manufacturing method of the printing base material of Claim 1 which sets the thickness precision of a resin cured material layer to 30 micrometers or less by the said process (b). The step (a) includes (d) a step of winding the sheet-like support around the surface of the cylindrical support, and (e) applying a resin composition onto the sheet-like support wound around the surface of the cylindrical support and applying a resin. forming a composition layer, after (f) curing the resin composition layer formed may include a step of forming a cured resin layer, and wherein step (c), (g) of the cured resin layer The manufacturing method of the printing base material of Claim 1 or 2 including the process processed into a sheet form by cut | disconnecting in the major axis direction of the said cylindrical support body. It resin composition of the step (e) is a photosensitive resin composition, according to claim 3 cured is cured by irradiation with high-energy radiation to the photosensitive resin composition of the step (f) Manufacturing method of printing substrate. The photosensitive resin composition is liquid at 20 ° C., has at least one molecular skeleton selected from a polycarbonate skeleton, a polyester skeleton, and an aliphatic hydrocarbon skeleton, and includes a urethane bond, an amide bond, and an imide bond. The method for producing a printing substrate according to claim 4, comprising a compound having at least one selected bond. The method of coating the resin composition on the sheet-like support is at least one method selected from a doctor blade coating method, a die extrusion method, a spray coating method, a gravure coating method, and a roll coating method. The manufacturing method of the printing base material in any one of Claims 3-5 . In step (b), the surface of the cured resin layer, cutting, grinding, using at least one method selected from grinding, the thickness of the cured resin layer, the step of adjusting the roughness Is carried out while rotating the cylindrical support in the circumferential direction. The method for producing a printing substrate according to any one of claims 1 to 6 . The printing base material produced using the method in any one of Claims 1-7. The printing substrate according to claim 8, which is used for applying a liquid electronic material or an optical material. A step of attaching the printing substrate according to claim 8 to a cylindrical printing cylinder of a printing machine, a step of attaching a liquid electronic material or optical material to the surface of the printing substrate, and transferring the material onto the substrate to be printed, A method for producing an electronic member or an optical member, comprising a step of immobilizing an electronic material or an optical material on the substrate to be printed. The electronic material or the optical material contains at least one compound selected from an aromatic hydrocarbon compound, a nitrogen-containing hydrocarbon compound, an ester compound, an amide compound, a glycol monoether compound, and a halogen-containing hydrocarbon compound as a total solvent component The method for producing an electronic member or an optical member according to claim 10, wherein the content is 20 wt% or more. The electronic member or optical member according to claim 10 or 11, wherein the substrate to be printed is at least one kind of substrate selected from a glass plate, a ceramic plate, a film, a metal plate, and paper. How to manufacture. The surface of the printing substrate is adjusted again while rotating the cylindrical support in the circumferential direction after mounting the printing substrate according to claim 8 used in the printing process on the cylindrical support. A method for regenerating a printing substrate,

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